Process for breaking petroleum emulsions



United States Patent 2,743,245 Patented Apr. 24, 1956 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Deb, a corporation of Delaware No Drawing. Application November 17, 1952, Serial No. 321,036

32 Claims. (Cl. 252-341) This invention relates to a process for breaking petroleum emulsions of the water-in-oil type and is characterized by subjecting such an emulsion to the action of a demulsifier, including certain acidic fractional esters which are disclosed in my co-pending application S. N. 321,031, filed November 17, 1952, and which are derived by esterifying an oxyalkylated amine-modified phenolaldehyde resin condensate with a polycarboxy acid.

Ignoring the preparation of the phenol-aldehyde resin per se the remainder of the reactions fall into three classes: (1) Condensation, (2) oxyalkylation, and (3) esterification.

The acidic fractional esters obtained in the manner herein described have utility for various purposes and particularly for the resolution of petroleum emulsions of the water-in-oil type. In this connection it should be noted that the polyhydroxylated reactant or reaction mixture may be obtained by combining a comparatively large proportion of the alkylene oxide, particularly propylene oxide, or a combination of propylene oxide and ethylene oxide, with a comparatively small proportion of the resin condensate. In some instances the ratio has been as high as fifty-to-one, i. e., the ultimate product of oxyalkylation contained about 2% of resin condensate and approximately 98% alkylene oxide. This was, of course, prior to the esterification step.

Momentarily ignoring the final step of esterfication this invention in a more limited aspect, as far as the reactants are concerned which, in turn, are subjected to oxyalkylation and then esterification, are, as previously noted,

'certain amine-modified thermoplastic phenol-aldehyde resins. Subsequent description in regard to the aminemodified resins employed is largely identical with the text as it appears in certain co-pending applications,

to wit, Serial No. 288,742, filed May 19, 1952, and Serial No. 301,803, filed July 30, 1952. For purpose of simplicity the invention, purely from a standpoint of the resin condensate involved, may be exemplified by an idealized formula as follows:

R R n R structure is derived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

RI HN in which R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals. The only limitation is that the radical should not be a negative radical, which considerably reduces the basicity of the amine, such as an aryl radical or an acyl radical. Needless to say, the two occurrences of R may jointly represent a single divalent radical instead of two monovalent radicals. This is illustrated by morpholine and piperidine. The intro.- duction of two such amino radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile etfect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another efiect is introduced, particularly another hydrophile eifect.

Referring again to the resins as such, it is worth noting that combinations, either resinous or otherwise, have been prepared from phenols, aldehydes, and reactive amines particularly monoamines.

Combinations, resinous or otherwise, have been prepared from phenols, aldehydes, and reactive amines, particularly amines having secondary amino groups. Generally speaking, such materials have fallen into three classes; the first represents non-resinous combinations derived from phenols as such; the second class represents resins which are usually insoluble and used for the purpose for which ordinary resins, particularly thermosetting resins are adapted. The third class represents resins which are soluble as initially prepared but are not heat-stable, i. e., they are heat-convertible, which means they are not particularly suited as raw materials for subsequent chemical reaction which requires temperatures above the boiling point of water or thereabouts.

As to the preparation of the first class, i. e., nonresinous materials obtained from phenols, aldehydes and amines, particularly secondary amines, see United States Patents Nos. 2,218,739, dated October 22, 1940, to Bruson; 2,033,092, dated March 3, 1936, to Bruson; and 2,036,916, dated April 7, 1936, to Bruson.

As to a procedure by which a resin is produced as such involving all three reactants and generally resulting in an insoluble resin, or in any event, a resin which becomes insoluble in presence of added formaldehyde or the like, see United States Patents Nos. 2,341,907, dated February 15, 1944, to Cheetham et al.; 2,122,433, dated July 5, 1938, to Meigs; 2,168,335, dated August 8, 1939, to I-Ieckert; 2,098,869, dated November 9, 1937, to Harmon et al.; and 2,211,960, dated August 20, 1940, to Meigs.

A third class of material which approaches the closest to the herein-described derivatives or resinous amino derivatives is described in U. 8. Patent No. 2,031,557, dated February 18, 1936, to Bruson.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols. This is a diiferentiation from the resins described in the aforementioned Bruson Patent No. 2,031,557, insofar that said patent discloses suitable resins obtained from metasubstituted phenols, hydroxybenzene, resorcinol, p,p'(dihydroxydiphenyl)dimethylmethane, and the like, all of which have at least three points of reaction per phenolic nuclei and as a result can yield resins which may be at least incipiently cross-linked even though they are apparently still soluble in oxygenated organic solvents 'or comparatively low molal produc 3 to 6 nuclei per'resin molecule. 'The resins employed in ture above theboiling point of water. I

fact, all the examples included subsequently employ temr else are heat-reactive insofar that they mayapproach insolubility or become insoluble due to the 'efiect-of heat;

or added formaldehyde, or both; 7 V 7 V The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. .As is well known, although one mayflstar't with difunctional .phenols, and depending on the procedure employed,'one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a di functional radical to a trifunctional radicaLor in terms of the resin, the molecule as a whole has a methylol-forming reactivity. greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an 'alkyl radical, "such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or

temperature of 80 to 90 C. There is no such limitation in the condensation procedure herein described for reasons which are obvious in light of'what has been said previously. a

What is said above deserves further amplification at this point for the reason that it may shorten what is said 7 subsequently in; regardto the production of the herein from-a para position to a meta position. For instance, in

the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reactioncan have three, and possibly morepointsof reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted 'me'thylol group.

Apparently there is no similar limitation in regard to the resins employed 'in the aforementioned Bruson'Patent 7 2,031,557, for the reason that one may prepare suitable resins from phenols of the kind already specified which invariably and inevitably would yield a resin having a functionality greater than two; in the ultimate resin molecule.

The resins herein employed are. soluble in. a 'nonoxygenatedhydrocarbon solvent, such as benzene or,

xylene. As pointed out in the aforementioned Bruson Patent 2,031,557, one of the objectives is to convert the phenol-aldehyde resins employed as raw'mate'rials in such described condensation products. As'f pointed out in the instant invention the resin selected is Xylene'or benzene 's'um'ption; that generally the amine will dissolve in one;

phase or the other. Although reactions of the kind herein described will begin atleast at comparatively low tem- .peratures, for instance, C;, C., or 0, yet the 3 such as alcohol, dioxane, various ethers' of reactiondoes not go to, completion exceptby. the use of thehighef temperatures The use of higher temperav I tures means, of course, that the condensation product obtained at the end ofthe reaction mustnot be heat-reactive Of course, onecan add an'oxygenated solvent 'glycols, or

I the-like, and producea homogeneous phase. ;If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience,

' but whether it is or'not, ultimately the temperature must a way as to'render them hydrocarbon soluble, i. e., soluble a in benzene. The original resinsof U. SfPatent 2,031,557 are selected on the basis of solubility in an oxygenated inertorganic solvent, such as alcoholor dioxanc. It is immaterial whether the resins here employed are soluble in dioxane or alcohol, but they must be soluble in benzene. The resins herein employed as raw materials must be ts having on the average the aforementioned U. S. Patent No. 2,031,557 apparently need not meet any such limitations. j

' The condensation products here obtained, whether in .the form of the free base or the salt, do not go over tothe insoluble stage on heating. This apparently is not trueof the materials described in'aforemention'edjBruson Patent 2,031,557 and apparently one of theobjectives with which theinvention is concerned, is to obtaina heatconvertible condensation product. .The' condensation product-obtained according to the present invention is heat stable and, in fact, one of its outstanding'qualitie's is that it can be subjected to oxyalkylation, particularly dxyethylation or ox'ypropylation, under conventional 'conditions, i.'e., presence of an alkaline catalyst, for example, but in any event at a temperature above C. :-without becoming an insoluble mass. 1

What has been saidpreviously in regardto heat stability,,particularly when employedas a reactant'i'or prepbintbf-imanufacture"of the condensation pro'ducts tliemfrelves insofar that in the condensation process employed in preparing the'comp'ounds described subsequently indetail/there 1s no'objection to the employingof' a tempera- -As a matter of Tperatures going up to to C. If one were using resins of the kind described in U. S.'Patent No. 2,031,557 it appears desirable and perhaps 'absolut elynecessary that'the temperature he kept relatively low,,f or instance, between 20 C. and-100 CL, and more specifically ata arati'o'n of derivatives, is'still important from the stand-p still pass within the zoneindicated elsewhere, -i.' e., somewhere above the boiling point of water unless some obvious equivalent procedure is used. 7

Any reference, as in the hereto appended claims, to the procedure employed in the'process is not intended to limit the methodor order in which the reactants are added, 7

commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons, As pointed outelsewhere it is my preference to dissolve the resin in a suitable solvent, and the amine, and then add the formaldehyde as a 37% solution. However,-all three reactants can be added in any order. I am inclined to believe that the presence of a basiccatalyst, such as the amine employed,,that thejformaldehyde produces methylol groups attached tolthe phenolic nuclei which, in turn, reactwith the amine. It'would be immaterial,

of course,-if the formaldehyde reacted with the amine'so as to introduce a methylol group attached to nitrogen itwould be immaterial if both types of compounds were formed whichr'eacted with'each other with the evolution a 'of a moleofformaldehyde available for further reaction.

Furthermore, a reaction could take place in which three 'difierent moleculesare simultaneously involved although, for theoretical reasons, that is less'likely. 'What is said 'herein in this respect is simply by-way of explanationto avoid any limitation in regard to the appended claims.

oxyalkylation -step an esterification step follows.

Since the amines herein employed are nonhydroxylated it is obvious the famine-modified resin is susceptible to' I oxyalkylation by virtue of the phenolic hydroxyl radicals,

"Referring to the'idealizedformula which. appeared previously it is obvious the oiryalkyl'atedderivativesjor at leasta substantial portion of them, could'be indicated in the following manner:

; n"o)..'rr

N-c H H n 11 which, in turn, wouldreactwith the resin molecule. Also,

Again it "is to'beemphasized that. at the end of the i 7 in which R"O is the radical of alkylene oxide, such as the ethoxy, propoxy or similar radicals derived from glycide, ethylene oxide, propylene oxide, or the like, and n is a number varying from 1 to 60, with the proviso that one need not oxyalkylate all the available phenolic hydroxyl radicals. In other words, one need only convert two phenolic hydroxyl radicals per resin molecule. Stated another way, n can be zero as wellas a whole number subject to what has been said immediately preceding, all of which will be considered in greater detail subsequently.

As far as the use of the herein described products goes for the purpose of resolving petroleum emulsions of the water-in-oil type, I prefer to use those which have suflicient hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the esters of the various condensation products may not necessarily be xylene-soluble although they are xylene-soluble in a large number of instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Reference is again made to U. S. Patent 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said immediately aforementioned patent the following test appears:

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-Water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with l-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sulficient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a Waterin-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 /2 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sutficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

' In many cases, there is no doubt as to the presence or absence ofhydrophile or surface-active characteristics in the products used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (subsurface-activity) tests for emulsifying properties or selfdispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent water-insoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with Water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines. Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

Having described the invention briefly and not necessarily in its most complete aspect, the text immediately following will be a more complete description with specific reference to reagents and the method of manufacture.

For convenience the subsequent text will be divided into six parts:

Part 1 is concerned with the general structure of the amine-modified resin condensates and also the resin itself, which is used as a raw material;

Part 2 is concerned with appropriate basic secondary monoamines free from a hydroxyl radical which may be employed in the preparation of the herein described amine-modified resins or condensates;

Part 3 is concerned with the condensation reactions involving the resin, the amine, and formaldehyde to produce the specific products or compounds;

Part 4 is concerned with the oxyalkylation of the products described in Part 3, preceding;

Part 5 is concerned with the conversion of the polyhydroxylated compounds or reaction mixtures described in Part 4, preceding, into acidic fractional esters by means of polycarboxy acids; and

Part 6 is concerned with the resolution of petroleum emulsions of the water-in-oil type bymeans of the acidic fractional esters previously described.

In the subsequent text, parts 1, 2 and 3 appear in substantially the same form as the text of the aforementioned copending application, Serial No. 288,742, filed May' 19, 1952, and also in aforementioned co-pending application, Serial No. 301,803, filed July 30, 1952. Part 4 is substantially the same as Part 4 as it appears in the last mentioned co-pending application. The text is so presented for both purpose of convenience and comparison. Similarly, Part 5 is substantially the same as it appears in aforementioned co-pending application, Serial No. 321,031, filed November 17, 1952.

PART 1 It is well known that one canreadily purchase on the In the above formula n represents a small whole number varying from l to 6, 7 or 8, or more, up to probably 1 7 open market, or prepare fusible, organic solvent-soluble, water-insoluble resin polymers of a compositionapproximated in an idealized form by the formula l or 12 units, particularly when the resin is subjected to "heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymerswherethe total number of phenol nuclei varies from 3 to 6, Le, n varies from 1'to4', 'R represents an aliphatic hydrocarbon substituent," generally an 7 7 alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalentbridge radical is shown as being derived from formaldehyde it may, of course, be derived from any. 1 other reactive aldehyde having 8 carbon atoms or-less. V 7

Because a resin is organic solvent-soluble does'not mean it is necessarily soluble in any organic solvent. This is particularly true wherethe resins arederived from tri- "functional phenols as previously noted. However, even when obtained from a difunctional. phenol, for instance para-phenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal -alc ohol, dioxane, or 'diethylglycol diethylether.

Sometimes a mixture of the two solvents(oxygen'ated and nonoxygenated) will serve. See'Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to DeGroote and Keiser. V

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, -or else prepare resins which are xylene I having not over 8 carbon atoms'and reactive toward said' phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenolbeing of the formula in wmeh'n is an aliphatic hydrocarbonradical having at least 4 carbon atoms and not more than 24 carbon atoms, a

and substituted in the 2,4,6 position.

, If one selected a resin of the kind just described previously-and reacted approximately one mole of the resin tworn oles of formaldehyde and two moles of. a basic nonhydroxylated secondary amine as specified, following the same idealized oversimplification previously referred to, the resultant product might be illustrated-thus:

t io

I The basicamine may be designated thus:

a 3 i 7 ii I V f R V In conducting reactions of this kind one does not necessarily obtain a hundred per cent yieldfor obvious-reasons.

Certain side reactions may take place. For instance, 2 moles of amine may combine'with' one mole of the aldehyde, or only one mole of the amine may combinewith the resin molecule, or even'to a very slight extent, if at all, 2 resin units maycombinewithout any amine in the reaction product, as indicated in the following formulas:

' on' "I'm I on H n a H, K

As has beenpoint ed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

"R' V R" n R in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For j '0 reasons ,which are obvious the condens'aiton product ob tained appears. to be described best in terms of the method of manufacture. i

As previously stated the preparation of resins, the kind herein employed as reactants, .is well known. See pret viously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst 'having neither acid nor basic properties 'in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In 'other'words, if preparedby'using a strong acid as a catalyst, such strong acid 'should'be neutralized. Similarly, if a strong base is used as a'catalyst it is preferable that the base be neutralized although I have found that sometimes'the reaction described proceeded more rapidly in the presence of a small amount of a free base. The

- much as a few l0 ths of a'percent. Sometimes moderate However, the mostdesirable procedure in practically everycase is to have the resin neutral. 0 V i V 'In :preparing resins one does not geta single'polymer, i. e.,- one having just '3. units, or just -4 units, or just '5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such. that it corresponds to a fractional value for was, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins' I found no reason for using other than those. which are :lowest in price and :mostreadily-availablecommercially. For puramount may be as small as a 200th of a percent and as TABLE I Ex. Position R derived R n of resin No. of R frommolecule Phenyl Para. Formaldehyde. 3. 5 992. 5 Tertiary butyL do d 3. 6 882. Secondary butyl- Ortho 3. 5 882. 5 Oyclohexyl 3. 5 1, 025. 5 Tertiary amyl 3. 5 959. 6a Mixed secondary 3. 5 805. 5

and tertiary am 7a.-.- Propyl 3. 5 805. 5 8a---- 3.5 1,036.5 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 3. 5 1, 49s. 5 3. 5 945. 5 3. 5 1, 022. 5 on 3.5 1, 330. 5 Tertiary butyl. 3. 5 1, 071. 5 1 Tertiary amyl 3. 5 1, 148. 5 N do 3.5 1,456.5 Propionalde- 3. 5 1,008. 5

hyde. 20a Tertiary amyl do -do 3. 5 1, 008.5 2la onyl d 3. 5 1, 393. 5 4. 2 996. 6 4. 2 1, 083. 4 4. 2 1, 430. 6 25a-.. Tertiary butyl 4. 8 1, 094. 4 26a Tertiary amyL 4. 8 1, 189.6 27a Nonyl 4.8 l, 570. 4

PART 2 As has been pointed out previously, the amine herein employed as a reactant is a basic secondary monoamine, and preferably a strongly basic secondary monoamine, free from hydroxyl groups whose composition is indicated thus:

\NH R! in which R represents a monovalent alkyl, alicyclic, arylalkyl radical and may be heterocyclic in a few instances as in the case of piperidine and a secondary amine derived from furfurylamine by methylation or ethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of course, amines such as dimethylamine, methylethylamine, diethylamine, dipropylamine, ethylpropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, and dinonylamine. Other amines include bis(1,3-dimethylbutyl)amine. There are, of course, a variety of primary amines which can be reacted with an alkylating agent such as dimethyl sulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc., to produce suitable amines within the herein specified limitations. For example, one can methylate alpha-methylbenzylamine, or benzylamine itself, to produce a suitable reactant. Needless to say, one can use secondary amines, such as dicyclohexylamine, dibutylamine or amines containing one cyclohexyl group and one alkyl group, or one benzyl group and one alkyl group, such as ethylcyclohexyl amine, ethylbenzylamine, etc.

Another class of amines which are particularly desirable for the reason that they introduce a definite hydrophile efiect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula in which X is a small whole number having a value of 1 or more, and may be as much as 10 or 12; n is an interger Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Compounds so obtained are exemplified by Other somewhat similar secondary amines are those of the composition R-O (0119a RO(OH2)s as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxyalpha-methylethylamine, and beta-phenoxypropylamine.

Other suit-able amines are the kind described in British Patent No. 456,517 and may be illustrated by The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is dilficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures Indeed, perhaps-no description is necessary over 'and above, what has been said previously, in light of subsequent examples. following details are included,

liquid at the early or low temperature stage'of reaction. if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, I have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable. petroleum hy drocarbon or'a mixture of such orjsim'ilar solvents. In-

de'ed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conductedin such a .way that theinitial reaction, and per- YStem. However, if desirable, one .can use an oxygen ated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used 'hapsl-the bulk'of the reaction tak es place ina polyphasei hydroxyacetic acid, etc. 'One'also may convert the finjished product into salts by simply adding a'stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the

selection of the solvent employed may depend in part whether or not the product at the completion of thereaction is to be converted into a salt form.

' In the next succeeding paragraph it is pointed out that V I, frequently it is convenient to eliminate all solvent, using a temperature of not over' 150 C. and employing vacuum, if required. This'applies, of course, only to those-circnmstances where itis desirableor necessary-to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used; The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e.,-the. use of the mostfeconomical solvent and also on three other factors, two of which have been previously 'mentioned;

'(a) is the solvent toiremain' in the reaction. mass with-I out removal? (b)' is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case=of .oxyalkylationl; and the'third factor is this, (0) is an eflort to be'madeto purify the reaction or one can use a comparatively non-volatile solvent such 7 V as dioxane or the diethyletlier of ethylene glycol. One 7 can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to mean initial resin which is soluble'only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which maybe the commercial product which is approximately 37%, orit may be diluted down to' about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to 'add a solid material instead of the liquid solution and, everything :else

being equal, the latter is apt to be more. economical. In

any event, water is present aswater of reaction. If the solvent is completely removedat the end of the process,

noproblem is involved if the material is used for any sub-' sequent reaction. However, if'the reaction mass is going to be subjected 'to some further reaction where the solvent may be objectionable, as in the case of ethyl or. hexyl alcohol, and if there is to be subsequent oxyalkylation, then,;obvious'ly, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, or course, is an advantage for reasons stated. i 7

Another factor, as far as the selectionof solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt ,to'be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with aresiri which is almost water-white in color, the products'obtained are almost invariably a dark red in color or at least a red-amber, or some color whichincludeslboth an'amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected .and on the amine selected the condensation product or reaction mass on a solvent-free basis may be'hard, resinous and comparable to the resin itself.

The products obtained, depending on .the reactants'selected, may be water-insoluble'or water-dispersible, or

'water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, bymaking a solution mass by the usual procedure as, for example, a waterwash to remove thewater-soluble unreacted .formaldehyde, if any, or awater-wash to remove any unreacted low molal solubleamine, employed and present after reaction? Such'procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, I have found xylene the most satisfactory solvent.

'I'have found no particular advantage in usinga low 7 temperature in the early stageof the reaction because,

and for-reasons explained,this is "not necessary although it doesapplyin some otherprocedures that, in a general way, bear some similarity to the present procedure.

.There'is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, forinstance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described; If a lower temperature reactionis-usedinitially the period is not critical,

in fact, it may be anything from' a few hoursup to 24 hours. I'have not found any case where it was necessary or even desirable to hold theflow temperature stage for.

morethan .24 hours; In fact, I am notconvinced there is any advantage in holding it'at this stage for more than 13 or 4 hours at-the most. This, again, is a matter of conin the acidified vehicle such as dilute solution, for inf venience largely for'one reason. In heating and stirring the'reactionmass there is a tendency for formaldehyde to be lost. 'Thus, if the reaction can be conducted at a lower temperature so as to use; up part of th'e'formaldehyde at such lower-temperature, then 'the'amount of unreacted formaldehyde is decreased subsequently and makes it eas ier toprevent any loss, Here, again, this lower temperature is not necessary by virtue; of'heat convertibility as 7 previously referred to."

If solvents and reactants are selected so the reactants and products of reaction are mutually solube,.then agitation is required only to-the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but Imay be convenient under certain circumstances.

On the oth er hand, if the products are not mutually soluble then agitation should be more vigorous for the the interfaces and the more vigorous the agitation the more interfacial area. -The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzeneor xylene. Refluxing shouldbe long enough to insure that the resinadded,

preferably in' a powdered form, is completely soluble. However, if the resin is prepared as such it may be added insolution form, just as preparation 'is described inaforementioned S. Patent 2,499,368. After theresin is in 13 complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a threephase system instead of a two-phase system although this would be extremely unusual. This solution, or mechani cal mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out I prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difficulty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. 'The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difiiculties are involved. I have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to -24 hours, I then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of amine or formaldehyde. At a higher temperature I use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. I then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 150 C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in I aforementioned U. S. Patent No. 2,499,3 68.

Needless to say, as far as the ratio of reactants goes I have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles of formaldehyde. In some instances 1 have added a trace of caustic as an added catalyst but have found no particular advantage in this. in other cases I have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases I have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible I have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surfaceactivity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted amine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1 b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a paratertiary butyl phenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei as the value for n which excludes the two external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a, preceding, were powdered and mixed with an equal weight of xylene, i. e., 882 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C., and 146 grams of diethylamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde was used as a 37% solution and 162 grams were employed, which were added in about 2 /2 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 20 hours. At the end of this period of time it was refluxed, 'using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time, and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within 2 to 3 hours after refluxing wasstarted. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately C., or slightly higher. The mass was kept at this higher temperature for about 4 hours and reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for the reaction was about 30 hours. In other examples it varied from 24 hours to 36 hours. Time can be reduced by cutting low temperature period to approximately 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

s of about to pounds.

stirring for a half-hour or longer.

'IiABLEII V i r v Strength of I Max. Ex. Resin Amt., formaldehyde Solvent used, eactmn distill. N 0. used grs. Amme used and amount soln. and and amt. i tune temp.,

- 7 C. (hrs amt. 0.

2a 882 Diethylamino, 146 grams"; 37W 162 g. 150 5a 480 Diothylamine, 73 grams.- 37%, 81 g. g 21 152 1011. 633 Diethylamine, 73 grams 30%, 100 g.;- 58 147 2a 441 Dibutylamine, 129 grams. 3 Y 32 149 5a 480 Dibutylamlne, 129 rams... 149 10a 633 Dibutylamine, 129 grams. 24 150 2a 882 Morpholine, 174 grams. 35 V 145 5a 480 Morpholine, 87 grams 24 156 10a 633 Morpholine, 87 grams 7 A 24 147 13a 473 Dloctylamine (di-2-ethyl 38 148 14a 511 Dloctylamine (d1-2-ethylhexylamine); 117 grams. 7 100 g... Y 30 146 15:1 665 Dioctylamine (di-Z-ethylhexylamine), 117 grams 37%,81-g. 24 150 2a 441 (CzH OC2H4OO HQNH, 250 grams 30%, 100 g 31 147 5a 480 (C2HOO2H4OC2H5)NH, 250 grams 30%, 100 g--- 36 148 9a 595 (C;H 0C H OG1H4)2NH, 250 grams. 37%, 81 5.--- 25 Y 145 2a, .441 (O346111oOOH;CH(CH O -(CHQ) GHCHmNH, 37%, Big 24 .161

' grams. u 5a 480 V (GgGIIIo-OOHQCH(CH;)O-(CH;)CHGH):NH, 37% 24 150 grams. 1411 511 (034611190CHCH OH90(CH3)CHGH:)NH, 30%, 100 g 25 146 grams. r 22a 493 (o gaoonqomooHwn oomoHngNH,. 37%, 81:55.. 24 140 grams. r 230' 542 31 330 CHaCHzOCHzCHz-OCHzOHahNH, 37%, 81 g. 2838 30 142 0 grams. 4 s 7 25a 547 ((gzoOH CH;OCHqOH5OCHzOHz)zNH, 37%, 81 g..- I 25-30 26 148 grams. 7 2a 441 (C1130CH3CH2CH1CH2-CH1OH2)2NH, 245 I 37%, 81 g 20-22 28 143 grams. 26a 595 (OHQOOH1CH2CH2CH2 CH2CH2)2NH, 245 30%, 100 g.-- 18-20 .25 146- grams. V r 27a 391 (CHzOOHgCH CH CHqOH)zNH, 98 grams- 30%, '50 g. 19-22 24 145 PART 4 30 continued 'oxylalkylation on a partial residual sample.

In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 3, the procedures employed are substantially the same as those conventionally used in carrying out oxyalkylations, and for this reason the oxyalkylation step will be simply illustrated by the following specific examples:

Example 0 V The oxyalkylation-susceptible compound employed is the one previously described and designated'as Example 1b. Condensate 1b was in turn obtained from diethylamine and the resin previously identified as Example 2d. Reference to Table I shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde;

10.56 pounds'of this'resin condensate were dissolved in: 5

8.8 pounds of solvent (xylene) along with one pound'of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately 125 C. to 130 C., and at a pressure The time regulator was set so as to inject theethylene oxide in approximately three hours and then continue The reaction went readily and. as a matter of fact, the ethylene oxide .could have been injected in less than anhours time andprob V ably the reaction could have been'completed without allowing for a subsequent stirring period. The speed of reaction, particularly at the low pressure, undoubtedly was due. in a-large measure to excellent agitation and also to the comparatively high concentration of catalyst; The

amount of ethylene oxide introduced was equal in weight tothe initial condensation product, to wit, 10.56 pounds. This represented a molal ratio of 24 moles of ethylene oxide per mole 'of condensate.

The theoretical molecular weight at the end of the 5 reaction period was 2112; A comparatively small sample. less than 50 grams, was withdrawnmerely for examination as far as solubility or emulsifying power was concerned. The amountwithdrawn was to. small that sequent data, or in the data presented in tabular form in subsequent Tables'3 and 4.

in innumerable comparable oxyalkylations I have with- The size of the autoclave employed was 25 gallons, 7

This was not the casein this particular series. Certain examples'were duplicated as 'hereinafter noted and sub-' 'jected to oxyalhylation with adifferent oxide. Certain Example 20 This example simply illustrates the further oxyalltylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptiblecompound, to wit, Example 1b, present at thebeginning of the stage was obviously the same as at the end of the prior stage (Example 10), to wit, 10.56 pounds The amount of oxide present in the initial step was, 10.56 pounds, the amount of catalyst remained the same, to .wit, one pound, and the amount of solvent remained the same; added was another 10.56 pounds, all addition of oxide in these various stages" being based on the addition of this particular amount. 7 Thus, at the end of the oxyethylation step the amount of oxide added was a total of'21.12. poundsand the molal ratio of'ethylene oxide to resin condensate was 48 to 1. The theoretical molecular.

weight was 3168., g

The maximum temperature during the operation was C. to C. The maximum pressure was in the range of-15"to12() jpounds. The time periodwas 3 /2 hours. f I

s Exampledc I Theoxyalkylation proceeded in the same manner described in Examples lc and 2c. There was no added solvent and no added catalyst. The oxide added was 10.56 pounds and the'total oxide in at the end of the oxyethylationstep was. 31.68 pounds; The molal ratio of oxideto condensate was 72 to 1. Conditions as far as temperature and pressure and time were concerned were allthe same as in examples 1c and 2c. The time period, as in Examples 10 and. 20, was 3 /2 hours.

I Example 4c no cognizance of this fact is included in the'data, or sub- 70 The oxyethylation was continued and the amount of oxide added againwas 10.56 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the end of the'reaction period was .5280. The molal ratio of oxide to condensate was 96 drawn a substantial portionat the end of each step'and 7510 1. Conditions as far as 'temperature and pressure The amount of oxide 1 17 were concerned werethe same as in previous examples. The time period was slightly longer, to wit, 4 hours. The reaction unquestionably began to slow up somewhat.

Example The oxyethylation continued with the introduction of another 10.56 pounds of ethylene oxide. No added solvent was introduced and, likewise, no added catalyst was introduced. Thetheoretical molecular weight at the end of the agitation period "was 6336, and the molal ratio of oxide to resin condensate was 124 to l. The time period, however, had increased to 5 hours even though the operating temperature and pressure remained the same as in previous example.

Example 60 The-sameprocedure was followed as in the previous six examples Without the addition of more caustic or more'solvent' The total amount of oxide introduced at the'end of the period was 72.93 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8448. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 6 hours.

Example 80 I This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 85.48 pounds. The theoretical molecular weight was 9604. The molal ratio of oxide to resin condensate .was 192. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was the same as in Example 7c, preceding, to wit, 6 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates'described previously. All these data have been presented in tabular form ina series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a l5-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial 5 but happened to be a matter of convenience. only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds through 40c were obtained by the use of ethylene oxide, whereas 41c through 80c were obtained by the use of propylene oxide alone.

Thus, in' reference to Table III it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that-ethylene oxide alone is employed, as happens tobe the case in Examples lc-through 400, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored 'where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particularseries the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples lc, 2c, 3c, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed. The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatvely small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV,-Examples 410 through 800 are the counterparts of Examples 10 through 40c, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4, 8, 11 and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by "d" numbers, 1d, 2d, 3d, etc. through and including 32d. They are derived, in turn, from compounds in the 0 series, for example, 350, 39c, 53c, and 620. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds lc through 400 were obtained by the use of ethylene oxide, it is obvious that those .obtained from 350, through 390, involve the use of ethylene oxide first, and propylene oxide afterward. ln'versely, those compounds obtained from 53c and'62c obviously came from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d,,3d, etc., the initial c series such as 35c, 39c, 53c and 62c, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to Wit, propylene oxide in 1a through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 350, consisted of the reaction product involving 10.5 pounds of the resin condensate, 15.84 pounds of ethylene oxide, 1.0 pound of caustic soda, and 8.8 pounds of'the solvent.

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i, e., the catalyst present from the first oxyalkylation ste'pplus added cata' Reference to. the solvent refers to theto'tal solveutaptesent,

i. el, that. from the first oxyalkylation step plus added.

used? along with either oneof thei-itwo; mmw:

tioned, or a "eombinatiomofi both ot theme The 'colors of the'products usually'vai'y' from a reddish amber tint to a definitely-red, and amber. The reason solvent, if any. I --is primarily that no efiortis made to obtain colorless In. this-.series, .in will be: noted that, the theoretical i i i i ll d, th pegins themselves. may b yellow, molecular weights are given prior to the oxyalkylation b -d k .ambeLCondensatmn f a 1 2 stepv and after'the oxyalkylation step, although the va1ue enous product invariablyyieldsza.d rken product thanthea the end of one step. is the'value at thebeginmng o original resinand usuallyhas areddish color. The solvent thenext step, except obviously at the very start the value employed if xyleneyaddsnmhing t9 thecolor but dependson the theoretical molecular weight at the end of use a darker colored aromatic, petroleum solvent. Oxythe. initial oxyalkylation step; 1'. e.,. oxyethylation for 1d alkylafion generally t dm g ield 1i l ter. olored productgg. through. 16d, and ox'ypropylat-ion for 17d through 32 and,themoreoxideemployed.flie1 igh athe M it will benoted': also. thatv under: the molal -atiov the product. Products can beptepaned. in1 which 0 80 values oflbotli oxides to.the= resin -condensate are included. 1 i a li h amber i h a ddi h i s h products The data given in regard to the operating conditions is can be decolorized by the use of clays, bleaching chars, substantially thexsame as before and appears in Table VI. etc. As far as use in demulsificatioriisconcerned or Iheproducts tesultingvfrom these procedures. may consome other "industrial'us'es, there is nojustification for the tain modest amounts, or have small amounts, of the solcost of bleaching'theproduct. vents as, indicated: by the: figures iu the. tables. If des red 20'- 'Li the oxyalkylated' derivatives'werenot used in subseth s v m y be em y l o a p quent esterifi'catio'n reactions, then alkalinity, whether due larly: vacuum distillation; Such dlStlllatlon also may reto an amino nit o en .at'oiii or added catalyst... would be. move traces or small amounts of uncombined oxide, 1f immaterial'for man purposes. For esterification it is present and volatile under the conditions employed. preferable that the alkalinity be elimii'iat'edjin, any one Obviously, in the use of ethylene oxide and propylen of'a' number of ways: (a) add an acid equiyalent to the oxide. infcombination one need. not first use oneoxide and added catalyst; ('li)".co11vert the catalystii'itosodium cliIothen the other, but one can mix the two oxidesand. thus. ride and the amine radical into. a h dr hlo ide; or obtairn what may be termedlan indifferent oxyalkylation, use an excess of the polycarbo'xy reactant even though a i. e., no attempt to selectively-add one and then the other, small percentage is wasted. fAll this is,-discussed.in detail or'any. other variant. .i inthe next section. M'Ol'C';C8l'flll examination of this Needless tosay, one could: start with ethylene oxide. and material. can be. madehy. methodsemploying. the well. then usepropylene oxide, and" then go back to ethylene known. Karl Fischer. reagents as; described in Aquametry, oxide; or, inversely, start with propylene oxide, then use. Smith. and.,-Mitchell, .J z", Interscience; Publishers,- New ethylene oxide, and then. go back topi'opyleneoxide; or, York,1l 9 48; one could use a combination in which. butyleneoxide is TABLE 111 Composition before Composition atend H UN 7 V Molalratio. 'g o-s' Ethyl. Pro 1 Catas01- Theo. Theo. o-s .5091; Pi-o' Ca ta so'i- I F g? cmpd, oxide, 0x1 0, Wet, Vfignt; 111(21- mole clilpq, 1 oxid8,-, 9x1 0, lyslg, I vent... ,fig g' giggfl No. lbs.v lbs. lbs. lbs. 5. w wt. bs. lbs. lbs. lbs. 7 lbs. nosinmresjn, oonden-concl'em sate sate- I -i.0 8.-8 .,1.0 8.8., 1.0, 8.8 1.0 '8.8 0; 1.0 8. 8 1.0 8.8- 1 1.0 8.8 V .1.0 8.8. 8.4 1.0- 8.8 1.0 8.8 r' 1.25 818' 1 .25.. 8.8 1.25 8.8 l 1.25 8.8. 1.25 8.8 9,750 10.84 80.72 125' 858 1.0 10:2 2, 568 12.84: 12.84. 1.0. 105 20:2

1.0 8,8. 3,168 10:50 21.12 1.0 88 45 1.0" 8.8 3,090- ,.iorss .2040; 1.0;.v ;;.-'8.8.:: 00:. 1.0., 8.: 4.224 10.00. 81.68 1.0. 8.8: 72 1.0 8.8 4,752 10. 50.90 1:0 8:8 84: 1:0 8.8" 5;,280. 10:50; 42.24 .1. 3 8.84.

' oxyalkylationeusceptiblm 25 fying polyhydroxylated reactants free from any nitrogen atom, particularly any basic nitrogen atom.

As stated in U. S. Patent No. 2,602,060, dated July 1, 1952, to De Groote, the production of esters, including acidic esters (fractional esters) from polycarboxy acids and glycols or other hydroxylated compounds, is well known. Needless to say, various compounds may be used such as the low molal ester, the anhydride, the acyl chloride, etc. However, for purpose of economy it is customary to use either the acid or the anhydride. A conventional procedure is employed. On a laboratory scale one can employ a resin pot of the kind described in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, and particularly with one more opening to permit the use of a porous spreader if hydrochloric acid gas is to be used as a catalyst. Such device or absorption spreader consists of minute Alundum thimbles which are connected to a glass tube. One can add a sulfonic acid such as paratoluene sulfonic acid as a catalyst. There is some objection to this because in some instances there is some evidence that this acid catalyst tends to decompose or rearrange polyoxyalkylated compounds, and particularly likely to do so if the esterification temperature is too high. In the case of polycarboxy acids such as diglycolic acid, which is strongly acidic, there is no need to add any catalyst.

In the case of highly oxyalklyated compounds, when nitrogen basicity can be ignored, or almost ignored, the use of hydrochloric gas has one advantage over paratoluene sulfonic acid and that is that at the end of the reaction it can be removed by flushing out with nitrogen, whereas there is no reasonably convenient means available of removing the para-toluene sulfonic acid or other sulfonic acid employed. If hydrochloric acid is employed one need only pass the gas through at an exceedingly slow rate so as to keep the reaction mass acidic. Only a trace of acid need be present. I have employed hydrochloric acid gas or the aqueous acid itself to eliminate the initial basic material. My preference, however, is to use no catalyst whatsoever and to insure complete dryness of the oxyalkylated amine-modified phenol-aldehyde resin as described in the final procedure just preceding Table VII.

The products obtained in Part 4, preceding, may contain a basic catalyst. Using highly oxyalkylated compounds, as ageneral procedure I have added an amount of half-concentrated hydrochloric acid considerably in excess of what is required to neutralize the residual catalyst. The mixture is shanken thoroughly and allowed to stand overnight. It is then filtered and refluxed with the xylene present until the water can be separated in a phase-separating tra As soon as the product is substantially free from water the distillation stops. This preliminary step can be carried out in the flask to be used for esterification. If there is any further deposition of sodium chloride during the reflux stage, needless to say, a second filtration may be required.

In any event, the product resulting from this pre-treatment is apt to be neutral or basic and particularly slightly basic. If a little more acid is used it may even by acidic. My preference, as pointed out previously, is that the product be neutral or slightly acidic. Oddly enough, if all the basicity is due to a basic nitrogen atom or more than one basic nitrogen atom since the resin condensate must invariably and inevitably have have at least two basic nitrogen atoms, I have found that in the stages of modest or heavy oxyalkylation the final product indicates that the basicity has been greatly reduced, possibly due to the hydroxylation or some other effect. Compare, for example, the reduced basicity of triethanolamine with that of ammonia. As previously noted, at the worse if all the catalyst has been removed or neutralized a little of the polycarboxy reactant may be lost.

Considering the resin condensates which are subjected to oxyalkylation, not only in the present application but also in the four co-pending applications, Serial Nos.

321,032, 321,033, 321,034, and'321,035, it is apparent I the situation becomes further complicated by the fact that an amine having one or more basic nitrogen atoms,

or even a cyclic structure, also may have hydroxyl radicals and possibly secondary nitrogen groups susceptable to acylation. Such amino groups are apt to disappear for obvious reasons on oxyalkylation, particularly after the initial step of oxyalkylation. Thus, what is said herein in regard to esterification applies with equal force and effect to substantially all hydroxylated compounds described, not only in this application but also in the four co-pending applications noted immediately above.

In any event, such oxyalkylated derivative described in Part 4 is then diluted further with suflicient xylene, decalin, petroleum solvent, or the like, so that one has obtained approximately a 65% solution. To this solution there is added a polycarboxylated reactant, as previously described, such as phthalic anhydride, succinic acid, or anhydride, diglycolic acid, etc., in the ratio of one mole of polycarboxy reactant for each available hydroxyl radical. The mixture is refluxed until esterification is complete as indicated by elimination of water or drop in car- 'boxyl value. Needless to say, if one produces a halfester from an anhydride such as phthalic anhydride, no

' water is eliminated. However, if it is obtained from diglycolic acid for example, water is eliminated. All such procedures are conventional and have been so thoroughly described in the literature that further consideration will be limited to a few examples and a comprehensive table.

Other procedures for eliminating the basic residual catalyst, if any, can be employed. For example, the oxyalkylation can be conducted in absence of a solvent or the solvent removed after oxyalkylation. Such oxyalkylated end-product can then be acidified with just enough concentrated hydrochloric acid to just neutralize the residual basic catalyst. To this product one can then add a small amount of anhydrous sodium sulfate (sutficient in quantity to take up any water that is present) and then subject the mass to centrifugal force so as to eliminate the dehydrated sodium sulfate and probably the sodium chloride formed. The clear, somewhat viscous, strawcolored amber liquid, or reddish-amber liquid, so obtained may contain a small amount of sodium sulfate or sodium chloride, but in any event, is perfectly acceptable for esterifica-tion in the manner described, subject to what has been said previously in regard to basicity due to the basic nitrogen atoms present.

It is to be pointed out that the products here described are not polyesters in the sense that there. is a plurality of both hydroxy reactant radicals and acid radicals; the product is characterized by having only one hydroxy reactant radical.

In some instances, and in fact, in many instances, I have found that in spite of the dehydration methods employed above a mere trace of water still comes through, and that this mere trace of water certainly interferes with the acetyl or hydroxyl value determination, at least when a number of conventional procedures are used and may retard esterification particularly where there is no sulfonic acid or hydrochloric acid present as a catalyst. There fore, I have preferred to use the following procedure: I have employed about 200 grams of the hydroxylated compound as described in Part 4, preceding; I have added about 200 grams of benzene, and then refluxed this mixture in the glass resin pot using a phase-separating trap until the benzene carried out all the water present as water of solution or the equivalent. Ordinarily this refluxing temperature is apt to be in the neighborhood of to possibly C. When all this water or moisture has been removed I also withdraw approximately 100 grams or a little less benzene and then add the required vents are sold by various oil refineries, and, as far as sol- I vent effect, act as if they were almost completely aromatic The in; aro- Water.

vions xamples,

is little or no reflux tempera The: same Time .estgriflr t 08 011,. 011 ,,w.. hrs;

. 5 7 0 67 8 75 867 71 5088086 8 8858m758875mm867m867D 66 86 8 mm m8 111 1 .be. allowed'.t o rem welLbe replaced by some decaliu or analkylated of course, is purely equires no elaboration. the following examples the. hydroxylated com- 1 weight. of xylene. and to 170 C., v or. somewhat. has been found that. on is complete.

usual. trap. arrangement. used. there ic acid and the amount bersof other e Max. est'erlfi- 08171061, I. te mga,

ch it swell ed. by distil1ation;..and parthenv the highboil definite or close range Boi on it,

ound was the one: pre

The amount employed was in.-a1 num in. Table VII immediately" Solvent '(xylene), grs;

0 03MB?L658233$M50$892H0296$378 650k50339535049677.2000

56 T mmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmummmmnmm lvent. such as imately 1.65

Example The time of. esterification was 8 hours Amt. of polycarb.

BIS;

these materials. are: for a purpose. such. cation the solventmi ht justa It the solvent. is to be. remov ticularly vacuum distillation,

5 matic petroleum solvent. might more expensive so decalin. which has a rather point. The removal of the. solvent :1. conventional procedure. an

10- Merely by way of illustrati use a. simple procedure, to w pound. is mixed with an. equa refluxed at approx higher, for 8 hours,, after. whi in. almost every instance reacti if formed, is separated by. the. Of. course, when anhydride. is; formation of water.

The hydroxyl'ated comp identified as Example 60. 200 grams. Theamount of xylenezwas lll grams. polycarboxy. reactant was: diglycol usedwas 12.7 grams; The max ture was 180 C.

the amount. of water out was 1.7 grams; procedure was. followed. all of which are included following:

TABLEVII I reactant,

in. the particular tisfactory are the:

242" c. -rnl., 244 C.

L, 252 C; 252" C.

ing is continued and,

wit, about 160. to hydride, needless he carboxy rehould appear. and

base-separating trap or. 190 .C., or even. goabove he solvent suband provided Theo. h yd. val. y a 0th. o. gig;

ml 'ml'., 248 C. ml ml. ml., 260 C. ml.,'2 64'- C. mll, 270 C. ml., 307 C'.

isextremely satisfactory, pro,

um distillation,

sidue. Actually, when of h. o h

ical distillation data;

, I simply. separate out another 5 to Ex. N0. Theom. of crnpd.

Ifthe .carboxy; reactant is an' an inated at the. above reaction temperature. Ifit is not eliminated jection to. a little re Ex. No. of acid ester imcharacter. Typ type 'I have employed andfound very sa following I.- B. P'., -5 ml., 200* C. 10mli, 209 C; '1'5'ml;, 215 C. 2'0 ml, 216 C. 25'ml., 220 C. 30ml 225 C. 351111;, 230 C; 40 m1, 234 C. 45 1111.,237" C.

After this'material is added, reflux of course, is at'a high temperature, to 17.0? C.. to; say,. nowater of reaction appears;. it t aet'ant. is; any acid, water of reaction 5 should be elim 10- cc. ofcbenzene by means. of the p and thus raise the temperature to 180 to:-200.. C.,.if need be. My preference. isznonto 200 C.

The use of. such. solvent vided one does not attempt to remove t sequently' except by vacu thereis no ob TABLE VIIContinued Max Amt. of Amt. t Time of Theo. Solvent esterifi- Ex. N0. of Ex. No. Theo. m. w. hyd. polycarb esterifi- Water acid ester of cm d. of h. c; cmpd. Paycarboxy reactant reactant (Xi/dens) canon cation, out, cc.

of h. c. grs. temp grs. gis. O hrs.

8d 6, 064 32. 4 200 Maleic anhydride 11. 3 211. 3 159 8d 6, 064 32. 4 200 Succinic anhydridc. 11. 5 211. 5 158 22d 1, 4116 13. 9 200 Diglyeolic acid 6. 64 205.8 180 2211 1, 4116 13.9 200 Phthalic anhydrrde. 7. 34 207. 3 176 22d 1, 4116 13. 9 200 Maleic anhydrlde 4. 85 204. 9 164 22d 1, 4116 13. 9 200 Aconltic acidfltn 8. 61 207. 2 175 2311 1, 5372 12. 79 200 Diglycolic acid. 6. 1 205. 3 182 2311 1, 5372 12. 79 200 Phthalic anhydride. 6. 75 206. 8 180 23!! l, 5372 12. 79 200 Maleic anhydride... 4. 45 204. 5 169 2311 1, 5372 12. 79 200 Adipic acid 6. 65 205. 8 175 2441 1, 6628 11. 8 200 Diglycolic acid.-.. 5. 65 204. 9 185 24d 1, 6628 11. S 200 6. 22 206. 2 183 2411 l, 6628 11. 8 200 4. 1 204. 1 175 2441 1, 6628 11. 8 200 4. 2 204. 2 173 PART 6 Oxyalkylated denvatrve, for example, the product of Gonventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents maybe used in a' water-soluble form, or in an oil-soluble form, (arm a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concen trations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

In practicing the present process the treating or demulsifying agent is employed in the conventional manner, well known to the art, described for example in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture, with or without the application of heat, and allowing the mixture to stratify.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, they may be diluted as desired with any, suitable solvent. For instance, by mixing 75 parts by weight of an oxyalkylated derivative, for example, the product of Example 52 with parts by weight of xylene and 10 parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the 'oxyalkylated product, and of course will be dictated in part by economic considerations, i. e., cost.

7 The products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates ,such combination is the following:

Example 5e, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent, is:

l. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weigth corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an alde hyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylcne oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the cmulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing processof' esterifying (A) an oxyalkylated aminemodified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being'ot the formula in which R is an aliphatic hydrocarbon radical havingjat least 4' and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction. being conducted at a temperature 'sufiiciently high to. eliminate water and below the pyrolytic point'of the reactants and resultants of reaction; with. the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reiactants'have contributed part of the ultimate molecule by virtue. of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further proviso that the ratio of reactants be approximately 1,2 and 2 respectively; and with the final proviso that the resinous condensation product re s'ulting fromthe process be heat-stable and oxyalkylationsusceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant" tooxyalkylated reactant being one mole of the former foreach hydroxyl. group present in the latter.

3'. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion 'to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-moditied phenol-aldehyde resin condensate with (B) a polycarboxy acid; and oxyalkylated condensate being obtained' lay-the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction: between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward; said phenol; said resinbeing formed in the substantial.

absence of trifunctional phenols; said phenol being. of the' formula in which R is an aliphatic hydrocarbon radical having atl'east4 and: not! more than 24 carbon atoms and substituted in the-2,4,6-position; (b) a basic nonhydroxylated secondary monoarnine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants'of' reaction, with the provisothat the condensationreactiom be: conducted so asto produce a significant portion ofv the resultant in which each of the three reactantshave: contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resin mole cule; with. theadded proviso that the ratio of reactants approximately 1,2 and 2, respectively; with the further: proviso'that said procedure involve the use of a solvent; and with the final proviso that the resinous condensae tion product resulting from the process be heat-stableand oxyalkylanon-susceptible; followed by an oxyalkylation step by means of an, alpha-beta alkylene oxide having; not morevthan. 4 carbon: atoms and selected from the class. consisting of. ethylene oxide, propylene. oxide, butylene oxide, glycide and methylglycide; the ratio-of.

polycarboxy acid reactant to oxyalkylated reactant being:

one. mole ofthe. former for each hydroxyl group premnt inthe latter.

4., Aprocess for breaking petroleum emulsions ofathe: water-in-oil type characterized. by subjecting the emulsion to the actionof. a demulsifier including synthetic by drophile products; said syntheticv hydrophileproducts; being: acidic. fractional esters obtained by the-manufactlm ing process ofesterifying, (A) an. oxyalkylated. modified phenol-aldehyde. resin condensate with (B); a.- polycarboxy acid; said oxalkylated condensatebeing obw tained'by the processof first condensing (a) an oxyal.-- kylation-susceptible, fusible, non-oxygenated organic sol-- vent-soluble, water-insoluble, low-stage phenol-formal. dehyde resin having an average molecular weight correspondingtoat: least-3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only= in'regard. to methylol-forming: reactivity; said resin: being derived by reaction between a difunctional. monohydi'ic: phenol. and. formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; saidphemi: being of. the: formula and- (0) formaldehyde; said condensation reaction beingconducted at a temperature sufficiently-high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to producea significant portion of the resultant in which each of the three reactants have' contributed part of the ultimate molecule by virtue of" a formaldehyde-derived methylene bridge. connecting the amino nitrogen atom with a. resin molecule; with the added; proviso that the ratio of reactants be approximately" 1,2 and 2, respectively; withv the'further proviso that'said procedure involvethe use of'a solvent; and'with'theifi'nal. proviso that the resinous condensation product resulting from the" process be heat-stable and oxyalkylanon-susceptible; followed by an oxyalk'ylation step hym'eans of an alpha-beta alkylene oxide havingnot more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide; and methylglycide; the ratio-of polycar boxy'acid' reactant to oxyalkylated reactant beingone mole of the former for each hydroxyl group present in the latter. a

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufilciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

6. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldein which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.-

7. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products; said synthetic hydrophile products being acidic fractional esters obtained by the manufacturing process of esterifying (A) an oxyalkylated amine-modified phenol-aldehyde resin condensate with (B) a polycarboxy acid; said oxyalkylated condensate being obtained by the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvenbsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of tnfunctional phenols; sad phenol being of the formula reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1,2 and 2, respectively; with the further provisothat said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and Qxyalky-lation-susceptibleg followed byr an oxyalkylation stepby means of an alpha-beta alkylene': oxide having.

not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide; the ratio of polycarboxy acid reactantto-oxyalkylated reactant being one mole of the former for each hydroxyl group present in the latter.

8. A-process for breaking 'pe'troleum"emulsions'of'the water-in-oi'htype characterized by subjecting th e emulsion to-the action of a demulsifi'er including synthetic hydrophile products; said synthetic hydrophile products bein'g'acidic fractional esters obtained by the manufacturing process'of esterifying (A) an oxyalkylated amine-modified'phenol-aldehyde resin'conde'nsate with (B); apolycarboxy acid; said oxyalkylated" condensate being obtained by the process of'first co'ndensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble; low-stagephenol-formaldehyde resin having an average molecular Weight corresponding'to atleast 3 and not'over 5 phenolicnuclei per resin' molecule; said resin being dit'uncti'onal only in regard 'to methylol-forming' reactivity; said resin being de rived" by reaction betw'een a-difunctional monohydric phenoland' formaldehyde; said resin *b'eingforme'd in the substantial absence of trifunctionalphenols; said phen'ol being of 'the'formula in which R is a para-substituted"aliphatic" hydrocarbon radical having at least 4'and not more than l4 carbon atoms; (1:) a basic nonhydrox'ylated secondary monoamine having not more than '32 carbon atoms in any group attached to the amino nitrogen atom, and ('c) formaldehyde; said condensation reaction being conducted" at a temperature above the boiling point 'of'water' and below 150 (3., with the proviso that the condensation reaction be conducted'sdas to produceasignificant portion of the resultant in which each ofthe threes re actants have contributed part 'of the ultimate molecule by" virtue of a formaldehyde-derived methylene bridge connecting' the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactantsbe approximately 1,2 and 2, respectively; with 'thefurther proe viso that said procedure involve the use of a solvent;' and with the final proviso'that the resinous condensation prod-' uct' resulting from the .process be. heat-stable and oxy alkylation-susceptibley followed'by an oxyalkylation step by means of an alpha-betaalkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycid; the ratio of polycarboxy acid reactant to oxyalkylated reactant being one mole of theformerfor each hydroxyl group present in the-latter.

9. Theprocess of claim 1 wherein the oxyalkylation step is limited to'the use of'both ethylene oxide and propylene oxide in combination, and the esterification step'is limited to the use ofa'dicarboxy acid having not a step is limited to-the use of both ethylene. oxide and propylene oxide in" combination, and the esterification step. is limited to the use of a dicarboxy'acid. having not over 8 carbon atoms. I h 13.. heprocess of claim 5 wherein the oxyalklation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited-to the use of a dicarboxy acid having not over 8 carbonatoms.

14. The process of claim 6 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over 8 carbon atoms. I

15; The process ofclaim- 7 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide incombination, and the esterification step is limited to the use of a. dicarboxy acid having not over8 carbon atoms.

16, The processof claim 8 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over 8 carbon atoms.

17. The process of claim 1 with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are" suflicie'nt to produce an emulsion when said xylene solution 'isshake'n' vigorously with 1 to 3volumes of water 181 The process of claim'2"with the proviso that the hydrophile propertiesof the product obtained'by oxyalkylation of the condensate prior to esterification employed in the formof a member'of the class consisting of (a) theanhydro base as-is, (b) the" free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

19. The process of claim 3 with the'proviso that the hydrophile properties of'the product'obtained by oxyalkylation ofthe condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficientto produce an emulsion when said xylene solution isshaken vigorously with l to 3 volumes of water.

20'. The process of claim14 with the proviso that th hydrophileproperties of the. product obtained by oxyalkylation' of. the condensate prior to esterification employed in the form of a-memberof-the class consisting-of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid; in. an equal weight of xylene are sufiicient to produce 'an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

21. The processof claim 5 with the'proviso that the hydrophile properties of the product obtained by oxyalkylation" of the condensate prior to esterification employed in the-form of a member of the classconsisting of. (a) the-anhydr'o base as is','(b) the free base, andtc) the salt ofhydroxy'acetic acid, in'an equal weight of xylene are sutficient to produce 'an -emulsionwhen said xylene solution is'shaken vigorously with l to 3 volumes of water.

22. The process of claim 6with'the proviso that the hydrophile properties of the product obtained by oxyal-' the salt of hydroxy acetic acid,- in-an equal weight'of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

23. The process of claim 7 with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

24. The process of claim 8 with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsionwhen said xylene solution is shaken vigorously with 1 to 3 volumes of water. i

25. The process of claim 1 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over eight carbon atoms; and with the proviso that the hydrophile properties of the product obtained by oxalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are suificient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

26. The process of claim 2 wherein the oxyalklation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over eight carbon atoms; and with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

27. The process of claim 3 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over eight carbon atoms; and with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

28. The process of claim 4 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over eight carbon atoms; and with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

29. The process of claim 5 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over eight carbon atoms; and with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

30. The process of claim -6 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over eight carbon atoms; and with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

31. The process of claim 7 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over eight carbon atoms; and with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufi'icient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

32. The process of claim 8 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination, and the esterification step is limited to the use of a dicarboxy acid having not over eight carbon atoms; and with the proviso that the hydrophile properties of the product obtained by oxyalkylation of the condensate prior to esterification employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS 2,031,557 Bruson Feb. 18, 1936 2,454,544 Bock et a1 Nov. 23, 1948 2,542,012 De Groote et al Feb. 20, 1951 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING SYNTHETIC HYDROPHILE PRODUCTS; SAID SYNTHETIC HYDROPHILE PRODUCTS BEING ACIDIC FRACTIONAL ESTERS OBTAINED BY THE MANUFACTURING PROCESS OF ESTERIFYING (A) AN OXYALKYLATED AMINE-MODIFIED PHENOL-ALDEHYDE RESIN CONDENSATE WITH (B) A POLYCARBOXY ACID; SAID OXYALKYLATED CONDENSATE BEING OBTAINED BY THE PROCESS OF FIRST CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 